N-halomethyl s-triazines



United States Patent 3,317,529 N-HALOMETHYL s-TRIAZINES Michael ThomasBeachem, Somerset, and John Christian Oppelt, Manville, NJ., assignorsto American Cyanamid Company, Stamford, Conn., a corporation of Mame NoDrawing. Filed July 7, 1964, Ser. No. 380,947

12 Claims. (Cl. 260-249.6)

This invention relates to a new class of compounds and to processes fortheir preparation. More particularly, it relates to N-halornethyls-triazines and their process of preparation and still more particularlys-triazines of the formulas set forth hereinbelow.

wherein X is chlorine or bromine; R is hydrogen, alkyl, aralkyl, aryl,or

A is a divalent hydrocarbon radical (polymethylene or phenylene); Y, Y YY and Y; are lower alkyl, CH OR or CH X; R is alkyl or alkene; and the Rand A radicals may be substituted by inert substituents such as cyano,halogen, etc.

The compounds of this invention are prepared by reacting an s-triazineof Formulas III and IV with certain acid halides such as acid chloridesor acid bromides in In Formulas III and IV above, R is hydrogen, alkyl,aralkyl, aryl or Y, Y Y Y and Y, are lower alkyl, CH X or -CH OR A is adivalent hydrocarbon radical; R is alkyl or alkenyl; and X is chlorineor bromine. The acid halide may be an acid bromide or acid chloride.

It will be observed from the formulas set forth above that thes-triazines of Formulas I, II, III and IV are N- substituted derivativesof guanarnines and melamine.

The s-tr-iazines of Formulas III and IV are N-alkoxymethyl derivativesof 2,4-diamino-s-tii-azines (guanamines) and of 2,4,6-triaminos-triazines (melamines), respectively. The non-nuclear (i.e., amido)ni-trogens of the s-triazines must be completely substituted byalkoxymethyl or lower alkyl groups. The s-triazines must be free of allactive hydrogens.

Suitable melamine derivatives of Formulas III and IV employable in theprocess of this invention includeN,N,N',N,N",N-hexakis(meth-oxymethyl)-2,4,6-

triamino-s-triazine,

N ',N',N"-trimethyl-N,N',N"-tris(methoxymethyl)-2,4,6-

triamino-s-triazine,

N,N,N,N"-tetramethyl-N',N"-bis-(methoxyrnethyl)-2,4,6-triarnino-s-triazine,

N,N,N,N,N",N-hexakis allyloxymethyl) -2,4,6-

triamino-s-triazine,

N,N,N',N"-tetramethyl-N',N"-bis octadecyloxymethyl)2,4,6-triamino-s-triazine,

and the like.

Examples of suitable guanamine derivatives which may be employed in theprocess of this invention are the following:

N,N,N,N-tetra.kis(methoxymethyl)-2,4-diamino-striazine,N,N,N,N'-tetrakis(methoxymethyl)-2,4-diamino-6- methyl-s-triazine,N,N,N',N'-tetrakis(methoxymethyl)-2,4-diarnino-6- ethyl-s-triazine,N,N,N,N-tetrakis(methoxymethyl)-2,4-diamino-6- octyl-s-triazine,N,N,N,N'-tetrakis (methoxymethyl -2,4-diamino-6- heptadecyl-s-triazine,N,N,N,N'-tetrakis(methoxymethyl)-2,4-diamino-6- phenyl-s-triazine,2,2'-hex-amethylenebis(N,N,N',N'-tetrakis[methoxymethyl]-4,6-diamino-s-triazine N,N,-N',N-tetrakis (-butoxyrnethyl-2,4-diamino-striazine,

and the like.

The acid halides which may be employed in the process of this inventionare chlorides and bromides. They include thionyl chloride, thionylbromide, phosgene, phosphorous pentachloride, phosphorous pentabromide,various acyl halides such as acetyl chloride, acetyl bromide, dec-anoylbromide, succinyl chloride, and alkyl halosul- 'fites, as for examplemethylchlorosulfite (CH O-SO-Cl) and the like.

In general, acid halides may be defined as halogen compounds of theformula where X is bromine or chlorine and D is or X. P, and R is alkylor aryl. The preferred acid halides are phosgene and thionyl chlorideand, of these, phosgene is preferred for reasons as will become apparenthereinafter.

The amount of acid halide employed in the process depends upon thenumber of halogen atoms in the acid halide and the properties of theby-products formed in the reaction. Thus, the amount depends upon thenumber of available halogen atoms present in the acid halide. It alsodepends upon the desired number of halogen atoms to be introduced intothe molecule. In the case of the mono-halogen acid halides, one mole isrequired for each chloromethyl group to be formed. In the case ofphosgene and phosphorous pentahalide, there is only one availablehalogen, and therefore one mole of acid halide is required for eachhalomethyl group to be formed. The by-product from phosgene is RiO-( )CIwhich does not react further with a -CH OR group, but decomposes to giveR X and carbon dioxide. The byproducts of phosphorous pentahalide arePOX and CH X and further reaction does not take place. The by-productfrom the reaction with thionyl chloride, on the other hand,

IMO--Cl which then partially decomposes to form sulfur dioxide and R 'Cland partially reacts further with another -CH OR group to form CH X.

Because of the properties of the by-products, phosgene in most cases ispreferred over thionyl chloride. Methyl chloroformate, the by-product ofphosgene, is stable and can therefore be recovered. Since methylchloroformate is stable, and therefore exactly one chlorine atom ofphosgene is available for the reaction with compounds of the FormulasIII and IV above, the amount of phosgene to be employed is readilycalculated.

In distinction, the by-product resulting from the use of thionylchloride is methyl chlorosulfite, which is unstable. Although a portionof the methyl chlorosulfite will react with the compounds of Formulas Iand II, the remainder decomposes. The amount that reacts and the amountthat decomposes depends upon the reaction conditions and are difficultto predict. Thus, there is a problem in determining how much thionylcompound should be employed. A further disadvantage is that it isdifficult to remove the last of the by-product sulfur dioxide from thereaction product.

The by-products from the reaction with acyl halide and alkylhalosulfites are esters of carboxylic acids and sulfurous acid,respectively.

The reaction of the compounds of Formulas III and IV with the acidhalide or halogen compound DX may be carried out with or without asolvent, though a solvent is preferred in that the reaction is morereadily controlled. Suitable solvents include benzene, toluene, xylene,chlorobenzene, chloroform and the like.

In carrying out the reaction, the acid halide or halogen compound may beadded to the molten s-triazine of Formulas III and IV or to a solutionof the 's-triazine at a temperature of from between and 100 C. andnormally the reaction mixture is heated at the final stages of reactionto a temperature of from between 40 and 120 C. until the reaction isessentially complete. The by-products and solvents, if used, may then beremoved by distillation, preferably in vacuo. The residue is theproduct.

While normally the reaction is carried out at atmospheric pressure, itmay be carried out at subatmospheric or superatmospheric pressure andmay be carried out in a batch or continuous manner.

The N-halomethyl s-triazines of this invention are useful as fiberreactive agents and provide means of achieving a number of specialeffects on fibrous substrates, as for example textile materials. Inparticular, when the compounds contain two or more chloromethyl groupsthey serve as cross-linking reactants imparting crease resistance andshrinkage control to such substrates as cellulosic and proteinaceoustextile materials. Moreover, the halomethyl s-triazines of thisinvention have all been found to possess antifungal activity againstTrichophyton mentagrophytes, Microsporum gypseum, and Chaetomiumglobsum: species of fungi.

In order that the present invention may be more fully understood, thefollowing examples are given primarily by way of illustration. Nospecific details or enumerations contained therein should be construedas limitations on the present invention except insofar as they appear inthe appended claims. All parts and percentages are by weight unlessotherwise specifically designated.

EXAMPLE 1 N-chloromelhyl-N,N,N,N",N"-pentakis(meth0xymethyl)-2,4,6-triamino-s-triazine IYKCHZO CH3): 0 N N EXAMPLE 2N,N-bis(chl0r0methyl) -N,N',N,N"-tetrakis(meth0xymethyl)-2,4,6-triamino-s-triazine CHzOCHa (OHHO CHzhN- The general procedure ofExample 1 is followed, using 19.5 parts ofN,N,N',N,N",N"-hexakis(methoxymethyl) 2,4,6-triamino-s-triazine, 6.0parts of thionyl chloride and about 40 parts of benzene as solvent.After removal of the volatile materials, the product is obtained as anoil which crystallizes on standing.

EXAMPLE 3N,N',N"-lris(chloromethyl)-N,N',N"-tris(methoxymethyl)-2,4,6-triamin0-s-triazineCHaOOHg CHgCI C N III CHZOCHI CHaOCHg To a solution of 19.5 parts (0.05mole) of N,N,N, N,N",N" hexakis(methoxymethyl) 2,4,6 triaminos-triazinein about 50 parts of benzene there is added at a temperature between andC. 5.0 parts (0.05 mole) of phosgene over about 30 minutes. The reactionmixture is then slowly heated to the reflux point and held at reflux forthree hours. After removal of the benzene by distillation in vacuo, thedesired product is recovered.

EXAMPLE 5 N,N',N"-tris(chlor0methyl) -N,N',N"-tris(meth0xymethyl)-2,4,6-triamino-s-triazine To 20 parts (0.051 mole) of moltenN,N,N',N',N", N",-hexakis(methoxymethyl-Z,4,6-triamino-s-triazine at atemperature between 80 and 90 C. there is added over 30 minutes 20 parts(0.204 mole) of phosgene. After removal of the volatile materials,including methyl chloroformate, by distilaltion in vacuo, the product isobtained as a residue analyzing for three atoms of chlorine per mole ofs-triazine.

EXAMPLE 6 N-bramomethyl-N,N',N'N",N"-pentakis(ethoxymethyl)-2,4,6-triamino-s-triazine CHzOCH N(CH2O (321-):

CH2OC2H5 To a solution of 4.75 parts (0.01 mole) of N,N,N, N,N"-hexakis(ethoxymethyl)-2,4,6-triamono-s-triazine in about 3 parts of toluene atabout 80 C. is added a solution of 1.23 parts (0.01 mole) of acetylbromide in about 2 parts of toluene. Ethyl acetate is evolved. Theremaining volatile materials are removed by distillation in vacuoleaving a crystalline residue. This is the desired product.

Calculated for C H BrN O N, 16.5. Found: N, 16.4.

EXAMPLE 7 N,N',N"-lris(chloromethyl)-N,N',N"-trimethyl-2,4,6-triamino-s-triazine 6 EXAMPLE 8 N,N'-bis(chloromethyl)-N,N,N",N"-tetramethyl-2,4,6- triamino-s-triazine IIMCHah CH3 N N CH:

\ H I NC\ N\ CIC 2 N CHaCl To a warm solution of 2.7 parts (0.01 mole)of N,N,N,N"-tetramethyl-N,N"-bis(methoxymethyl)-2,4,6-triamino-s-triazine in about 5 parts of benzene there is added asolution of 3.3 parts (0.0277 mole) of thionyl chloride in about 5 partsof benzene. After the reaction mixture has refluxed for about 30minutes, the volatile materials are removed by distillation in vacuo.The residue solidifies on standing and is the desired product.

Calculated for C H CI N N, 29.69. Found: N, 29.32.

EXAMPLE 9 N,N'-bis(chl0r0methyl) -N,N',N",N"-telramethyl-2,4,6-triamino-s-triazine EKCHg):

e t I F NC N CIC 2 N CHzCl To a solution of 2.06 parts (0.0044 mole) ofN,N,N, -tetramethyl-N',N"-bis (octyloxymethyl) -2,4,6-triamino-s-triazine in about 10 parts of benzene there is added 1.19parts (0.01 mole) of thionyl chloride. After refluxing for a short timeto expel sulfur dioxide, the reaction mixture is distilled in vacuo toremove benzene and octyl chloride. The crystalline residue is thedesired product according to the infrared spectrum when compared withthe product of Example 8.

EXAMPLE 10 N,N,N',N'-tetrakis(chloromethyl -2,4-diamino-s-triazine To asolution of 50 parts (0.42 mole) of thionyl chloride in about 25 partsof benzene is added a solution of 28.7 parts (0.1 mole) ofN,N,N',N'-tetrakis(methoxymethyl)-2,4-diamino-s-triazine in about 15parts of benzene. The reaction mixture is heated while sulfur dioxideand methyl chloride are evolved. The remaining volatile materials areremoved by vacuum distillation. The residue is the desired product.

EXAMPLE 11 N,N-bis(chl0romethyl) -N,N-bis(methoxymethyl)-2,4-diamin0-6-ethyl-s-triazine To a solution of 6.30 parts (0.02 mole) ofN,N,N,N'- tetrakis(methoxymethyl)-2,4,-diamino-6-ethyl-s-triazine inabout 10 parts of benzene there is added a solution of 12.0 parts 0.1mole) of thionyl chloride in 10 parts of benzene while heating thereaction mixture. After removal of the volatile materials bydistillation in vacuo, the residue solidifies. This is the desiredproduct.

7 EXAMPLE 12 N,N'-bis(br0momethyl)-N,N-bis(meth0xymethyl)-2,4-diamino-G-phenyl-s-triazine To a solution of 18.17 parts (0.05 mole) ofN,N,N,N- tetrakis(methoxyrnethyl) 2,4 diamino 6 phenyl striazine inabout 20 parts of toluene at 80 C. there is added a solution of 7.37parts (0.06 mole) of acetyl bromide in about 5 parts of toluene. Theby-product, methyl acetate, and toluene are removed by distillation. Theresidue on trituration with ether yields the product as a solid.

EXAMPLE 13 N,N,N',N'-tetrakis(bromomethyl -2,4-diamin-6-phenyl-s-triazine To a solution of 9.08 parts (0.025 mole) of N,N,N',N-tetrakis(methoxymethyl) 2,4 diamino 6 phenyl striazine in about 175parts of benzene there is added a solution of 16.0 parts (0.12 mole) ofacetyl bromide in about 25 parts of benzene. The reaction mixture isheated at the reflux temperature for about one hour. After removal of aportion of the solvent by distillation, the residue is cooled, and theproduct is separated by filtration.

Calculated for C H Br N C, 28.1; H, 2.33; Br, 57.1; N, 12.5. Found: C,28.1; H, 2.70; Br, 57.3; N, 13.0.

EXAMPLE l4 2,2-0ctamethylenebis[N,N-bis(chloromethyl)-N,N-bis(meth0xymethyl)-4,6-diamin0-s-triazine] To a solution of 3.2 parts(0.005 mole) of 2,2-octamethylenebis[N,N,N,N tetrakis(methoxymethyl) 4,6-diamino-s-triazine] in about 5 parts of benzene there is added asolution of 6.0 parts (0.05 mole) of thionyl chloride in about 5 partsof benzene. The reaction mixture is heated for about 30 minutes and thevolatile materials are removed by distillation in vacuo. The residualoil solidifies on standing to give the desired product.

Calculated for C H Cl N O C, 44.4; H, 6.3; N, 19.9, Found: C, 44.4;H,6.4; N, 19.9.

We claim: 1. A compound selected from the group consisting of thosehaving the formulas and wherein X is selected from the group consistingof chlorine and bromine; R is selected from the group consisting ofhydrogen, alkyl of less than 20 carbon atoms, carbocyclic aryl loweralkyl, carbocyclic aryl and A is a divalent hydrocarbon radical of lessthan 10 carbon atoms; Y, Y Y Y and Y are selected from the groupconsisting of lower alkyl, CH OR and CH X; and R is selected from thegroup consisting of alkyl of less than 20 carbon atoms and loweralkenyl.

2. N chloromethyl N,N',N,N",N" pentakis(methoxymethyl-2,4,6-triamino-s-triazine.

3. N,N bis(chloromethyl) N,N',N",N tetrakis(methoxymethyl)-2,4,6-triamino-s-triazine.

4. N,N,N tris(chloromethyl)-N,N,N"-tris(methoxymethyl)-2,4,6-triamino-s-triazine.

5. N,N bis(chloromethyl)N,N-bis(methoxymethyl)-2,4-diamino-6-ethyl-s-triazine.

6. N,N-bis(chloromethyl) N,N' yl)-2,4-diamino-6-phenyl-s-triazine.

7. N-bromomethyl N,N,N,N,N" pentakis(ethoxymethyl)-2,4,6-triamino-s-triazine.

8. N,N,N-tris(chloromethyl) N,N',N" trimethyl-2,4,6-triamino-s-triazine.

9. N,N'-bis(chloromethyl) 2,4,6-triamino-s-triazine.

10. N,N'-bis(chloromethyl) N,NN",N"-tetramethyl-2,4,6-triamino-s-triazine.

11. N,N,N,N'-tetrakis(bromomethyl) 2,4-diamino-6- phenyl-s-triazine.

12. 2,2 octamethylenebis[N,N bis(chloromethyl)- N,N-bis (methoxymethyl-4,6-diamino-s-triazine].

- bis(methoxymeth- Theilheimer: Synthetic Methods of Organic Chemistry,vol. 7, Interscience Pub., NY. (1953), No. 528, page 226.

WALTER A. MODANCE, Primary Examiner.

JOHN M. FORD, Assistant Examiner,

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF THOSE HAVING THEFORMULAS